Method and catalyst composition for producing aromatic carbonates

ABSTRACT

A method and catalyst composition for economically producing aromatic carbonates from aromatic hydroxy compounds is disclosed. The present invention provides a method for carbonylating aromatic hydroxy compounds, comprising the step of contacting at least one aromatic hydroxy compound with oxygen and carbon monoxide in the presence of a halide-free carbonylation catalyst composition comprising an effective amount of at least one Group 8, 9, or 10 metal source, an effective amount of a first inorganic co-catalyst comprising at least one Group 14 metal source, an effective amount of a salt co-catalyst, and optionally an effective amount of a second inorganic co-catalyst selected from the group consisting of a Group 4 metal source, a Group 7 metal source, a Group 11 metal source, and a lanthanide element source, and optionally an effective amount of a base. A significant advantage of the present method and catalyst compositions is that no halide is present or required in the reaction mixture for catalytic activity.

BACKGROUND OF THE INVENTION

[0001] The present invention is directed to a catalyst composition andmethod for producing aromatic carbonates through the carbonylation ofaromatic hydroxy compounds.

[0002] Aromatic carbonates find utility, inter alia, as intermediates inthe preparation of polycarbonates. For example, a popular method ofpolycarbonate preparation is the melt transesterification of aromaticcarbonates with bisphenols. Various methods for preparing aromaticcarbonates have been previously described in the literature and utilizedby industry. A method that has enjoyed substantial popularity in theliterature involves the direct carbonylation of aromatic hydroxycompounds with carbon monoxide and oxygen catalyzed by at least oneGroup 8, 9 or 10 metal source. Further refinements to the carbonylationcatalyst composition include the identification of co-catalysts.

[0003] The utility of the carbonylation process is strongly dependent onthe number of moles of desired aromatic carbonate produced per mole ofGroup 8, 9, or 10 metal utilized (i.e. “catalyst turnover number or‘TON’”). Consequently, much work has been directed to the identificationof efficacious catalyst compositions that increase the catalyst turnovernumber.

[0004] Carbonylation catalyst literature lauds the effectiveness ofhalide salts, particularly bromide salts, in catalyst compositions forimproving catalyst TON's. While it is true that catalyst compositionsthat contain halide salts have historically exhibited high activity,there are drawbacks to using halide in a carbonylation reaction. Forexample, when used to carbonylate phenol, bromide anions are consumed inthe process, forming undesirable brominated byproducts, such as 2- and4-bromophenols and bromodiphenylcarbonate.

[0005] It would be desirable to identify catalyst compositions thatwould minimize consumption of components or perhaps that would omitcomponents such as halide. It would also be desirable to increaseselectivity toward the desired carbonate product and minimizingformation of undesirable halogenated byproducts.

[0006] As the demand for high performance plastics has continued togrow, new and improved methods of providing product are needed to supplythe market. Consequently, a long felt, yet unsatisfied need exists fornew and improved methods and catalyst compositions for producingaromatic carbonates and the like.

SUMMARY OF THE INVENTION

[0007] Accordingly, the present invention is directed to a method andcatalyst composition for producing aromatic carbonates. In oneembodiment, the present invention provides a method for carbonylatingaromatic hydroxy compounds, comprising the step of contacting at leastone aromatic hydroxy compound with oxygen and carbon monoxide in thepresence of a carbonylation catalyst composition comprising an effectiveamount of at least one Group 8, 9, or 10 metal source, an effectiveamount of at least one inorganic co-catalyst comprising a Group 14 metalsource, and an effective amount of at least one salt co-catalyst,wherein the carbonylation catalyst composition is free of a halidesource.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0008] The present invention is directed to a carbonylation method andcatalyst composition for producing aromatic carbonates. The constituentsof the carbonylation catalyst composition are defined as “components”irrespective of whether a reaction between the constituents occursbefore or during the carbonylation reaction. Thus, the catalystcomposition typically includes the components and any reaction productsthereof. In one embodiment, the method includes the step of contactingat least one aromatic hydroxy compound with oxygen and carbon monoxidein the presence of a carbonylation catalyst composition comprising aneffective amount of at least one Group 8, 9, or 10 metal source, aneffective amount of an inorganic co-catalyst comprising at least oneGroup 14 element source, and an effective amount of at least one saltco-catalyst, wherein the carbonylation catalyst composition is free of ahalide source. Unless otherwise noted, the term “effective amount,” asused herein, includes that amount of a substance capable of yielding thedesired aromatic carbonate, or also includes that amount of a substancethat increases the selectivity of any one of the starting reagents (e.g.oxygen, carbon monoxide, and aromatic hydroxy compound) towards thedesired aromatic carbonate. In another embodiment, the method includesthe step of contacting at least one aromatic hydroxy compound withoxygen and carbon monoxide in the presence of a carbonylation catalystcomposition that comprises an effective amount of at least one Group 8,9, or 10 metal source, an effective amount of at least one firstinorganic co-catalyst comprising at least one Group 14 element source,an effective amount of at least one second inorganic co-catalystselected from the group consisting of a Group 4 metal source, a Group 7metal source, a Group 11 metal source, and a lanthanide element source;and an effective amount of at least one salt co-catalyst, wherein thecatalyst composition is free of a halide source. In yet anotherembodiment, the method includes the step of contacting at least onearomatic hydroxy compound with oxygen and carbon monoxide in thepresence of a carbonylation catalyst composition that comprises aneffective amount of at least one Group 8, 9, or 10 metal source, aneffective amount of at least one first inorganic co-catalyst comprisingat least one Group 14 element source, an effective amount of at leastone second inorganic co-catalyst selected from the group consisting ofGroup 4 metal sources, and lanthanide element sources; an effectiveamount of at least one salt co-catalyst, and an effective amount of atleast one base, wherein the catalyst composition is free of a halidesource

[0009] Any aromatic hydroxy compound, which is convertible to acarbonate ester, is suitable in the present invention. For example,suitable aromatic hydroxy compounds include, but are not limited to,monocyclic, polycyclic or fused polycyclic aromatic monohydroxy orpolyhydroxy compounds having from about 6 to about 30, and preferablyfrom about 6 to about 15 carbon atoms. Illustrative examples include butare not limited to phenol, alkylphenols, alkoxyphenols, biphenols,bisphenols, and salicylic acid derivates such as methyl salicylate.

[0010] The carbonylation catalyst composition contains at least onecatalyst component selected from Group 8, 9 or 10 metal sources. TypicalGroup 8, 9 or 10 metal sources include ruthenium sources, rhodiumsources, palladium sources, osmium sources, iridium sources, platinumsources, and mixtures thereof. The quantity of the Group 8, 9, or 10metal source is not limited in the process of the present invention. Theamount employed should be about 1 gram of Group 8, 9, or 10 metal per100 grams to, 1,000,000 grams of aromatic hydroxy compound (i.e. about 1part per million (ppm) to about 10,000 ppm of Group 8, 9, or 10 metal).For example, about 1 ppm to about 1000 ppm of Group 8, 9, or 10 metal issuitable. In one embodiment of the present invention about 1 ppm toabout 30 ppm of Group 8, 9, or 10 metal is used. A typical Group 8, 9,or 10 metal source is a palladium source. The palladium source used istypically in the Pd (II) oxidation state at the beginning of thereaction. Alternatively, a palladium compound in either the Pd(0) orPd(IV) oxidation states can be used. As used herein, the term “compound”includes inorganic, coordination and organometallic complex compounds.The compounds are typically neutral, cationic, or anionic, depending onthe charges carried by the central atom and the coordinated ligands.Other common names for these compounds include complex ions (ifelectrically charged), Werner complexes, and coordination complexes. AGroup 8, 9, or 10 metal source can be employed in a homogeneous formthat is substantially soluble in the reaction media or in aheterogeneous form which is substantially insoluble in the reactionmedia, including supported or polymer bound species. Examples ofsuitable palladium sources include, but are not limited to, palladiumsponge, palladium black, palladium deposited on carbon, palladiumdeposited on alumina, palladium deposited on silica, palladium sulfates,palladium nitrates, palladium carboxylates, palladium oxides, palladiumacetates, palladium salts of β-diketones, palladium salts ofβ-ketoesters, and palladium compounds containing any of the followingligands: carbon monoxide, amine, nitrite, nitrile, isonitrile,phosphine, phosphite, phosphate, alkoxide, alkyl, aryl, silyl or olefin.In one embodiment palladium(II) acetate is used. In another embodimentpalladium(II) 2,4-pentanedionate is used.

[0011] The carbonylation catalyst composition in the present inventionfurther contains an effective amount of at least one first inorganicco-catalyst (IOCC) comprising at least one Group 14 element source. Asused herein, the term “inorganic co-catalyst” includes any catalystcomponent that contains a metal element, which is present in thecatalyst composition in addition to the Group 8, 9 or 10 metal source.The Group 14 element source is at least one selected from the groupconsisting of silicon, germanium, tin, and lead. In an alternativeembodiment of the invention, a second IOCC selected from the groupconsisting of Group 4 metal sources, and lanthanide element sources, isalso present in the catalyst composition. The Group 4 metal source is atleast one selected from the group consisting of zirconium, hafnium, andtitanium. The Group 7 metal source is at least one selected from thegroup consisting of rhenium and manganese. The Group 11 metal source isat least one selected from the group consisting of silver, gold andcopper. The lanthanide element source is at least one selected from thegroup consisting of praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, and lutetium and preferably cerium. Suitable forms of Group14, Group 4, Group 7, Group 11, and lanthanide IOCC's include, but arenot limited to, elemental metals, metal salts, metal compounds in stableoxidation states, and precursors thereof which form catalytically activemetal species under the reaction conditions. The compounds are typicallyneutral, cationic, or anionic, depending on the charges carried by thecentral atom and the coordinated ligands. Illustrative examples of Group14, Group 4, Group 7, Group 11, and lanthanide IOCC's include but arenot limited to oxides, carboxylates, acetates, salts of β-diketones,salts of β-ketoesters, nitrates, and compounds containing any of thefollowing ligands: carbon monoxide, amine, nitrite, nitrile, isonitrile,cyanide, phosphine, phosphite, phosphate, alkoxide, alkyl, aryl, silylor olefin. The IOCC's are typically initially soluble in the reactionmixture, and typically remain soluble or become at least partiallyinsoluble during the course of the reaction, or they are typicallyinitially insoluble in the reaction mixture, and remain either insolubleor become at least partially soluble during the course of the reaction.Alternatively, the IOCC's are typically supported or polymer-bound witha variety of support media, including but not limited to carbon,alumina, silica, and zeolites.

[0012] In addition to the Group 8, 9, or 10 metal catalyst, at least oneGroup 14 element is present as a first IOCC in the carbonylationcatalyst composition. In one embodiment the Group 14 element is lead.Illustrative examples of suitable lead sources include, but are notlimited to, lead oxides such as lead(II) oxide, tri-lead tetraoxide, andlead(IV) oxide, lead carboxylates such as lead acetate and leadproprionate, inorganic lead salts such as lead nitrate and lead sulfate,alkoxy and aryloxy lead compounds such as lead methoxide and leadphenoxide, lead β-diketone compounds such as lead(II)2,4-pentanedionate, organometallic lead compounds having at least onelead-carbon bond, e.g., alkyl lead compounds such as tetraethyllead(IV),and lead compounds containing any of the following ligands: carbonmonoxide, amine, nitrite, nitrile, isonitrile, cyanide, phosphine,phosphite, phosphate, alkoxide, alkyl, aryl, silyl or olefin. In oneembodiment, the lead source is lead(II) oxide. In another embodiment thelead source is tetraethyllead(IV). Mixtures of lead compounds are alsosuitable.

[0013] In an alternative embodiment, in addition to the first IOCCcomprising a Group 14 metal source, a second IOCC is typically presentin the carbonylation catalyst composition. The second IOCC is at leastone member selected from the group consisting of a Group 4 metal source,a Group 7 metal source, a Group 11 metal source, and a lanthanideelement source.

[0014] An example of a Group 4 metal source is a titanium source.Illustrative examples of titanium sources include, but are not limitedto, titanyl oxides, titanium alkoxides, titanium aryloxides, titaniumnitrates, titanium carboxylates, and titanium sulfates. Additionalexamples of titanium sources include titanium compounds containing anyone of the following ligands: carbon monoxide, amine, nitrite, nitratenitrile, isonitrile, cyanide, phosphine, phosphite, phosphate, alkoxide,alkyl, aryl, silyl, olefin, β-diketone, or β-ketoester. In oneembodiment the titanium source is titanium(IV) oxide 2,4-pentanedionate.Mixtures of titanium sources are also suitable.

[0015] An example of a Group 7 metal source is a manganese source.Illustrative examples of manganese sources include but are not limitedto manganese nitrates, manganese carboxylates, manganese sulfate, andmanganese compounds containing any one of the following ligands: carbonmonoxide, amine, nitrite, nitrile, isonitrile, cyanide, phosphine,phosphite, phosphate, alkoxide, alkyl, aryl, silyl, olefin, β-diketone,or β-ketoester. In one embodiment the manganese source is manganese(III) 2,4-pentanedionate. Mixtures of manganese sources are alsosuitable.

[0016] An example of a Group 11 metal source is a copper source.Examples of copper sources include but are not limited to copper oxides,copper alkoxides, copper aryloxides, copper nitrate, coppercarboxylates, copper sulfate, and copper compounds containing any one ofthe following ligands: carbon monoxide, amine, nitrite, nitrile,isonitrile, cyanide, phosphine, phosphite, phosphate, alkoxide, alkyl,aryl, silyl, olefin, β-diketone, or β-ketoester. In one embodiment thecopper source is copper(II) 2,4-pentanedionate. Mixtures of coppersources are also suitable.

[0017] An example of a lanthanide element source is a cerium source.Illustrative examples of cerium sources include, but are not limited to,cerium oxides, cerium alkoxides, cerium aryloxides, cerium nitrate,cerium carboxylates, cerium sulfate, and cerium compounds containing anyone of the following ligands: carbon monoxide, amine, nitrite, nitrile,isonitrile, cyanide, phosphine, phosphite, phosphate, alkoxide, alkyl,aryl, silyl, olefin, β-diketone, or β-ketoester. In one embodiment thecerium source is cerium(III) acetate. In another embodiment the ceriumsource is cerium(III) 2,4-pentanedionate. Mixtures of lanthanidessources, including but not limited to, cerium sources are also suitable.

[0018] In one embodiment of the present invention, in addition to theinorganic components at least one organic co-catalyst salt is alsopresent. As used herein, the term “organic co-catalyst salt” includesany catalyst component which is present in the catalyst composition, inaddition to the Group 8, 9 or 10 catalyst and any IOCC source, whichcomprises an anion selected from the group consisting of acetate,carboxylate, benzoate, sulfate, nitrate, tetraarylborate,alkylsulfonate, arylsulfonates, or cyanide.

[0019] Typical organic co-catalyst salts contain a cation selected fromthe group consisting of an alkali metal cation, an alkaline-earth metalcation, guanidinium, or an onium cation. Examples of onium cationsinclude ammonium cations, phosphonium cations, and sulfonium cations. Invarious embodiments the organic co-catalyst salts used include sodiumcarboxylates (e.g. sodium acetate), tetraalkylammonium carboxylates(e.g. tetrabutylammonium benzoate), tetraalkylammonium sulfates (e.g.tetrabutylammonium sulfate), tetraalkylammonium nitrates (e.g.tetrabutylammonium nitrate) tetraalkylammonium tetraarylborates (e.g.tetrabutylammonium tetraphenylborate), tetraalkylammonium sulfonates,(e.g. tetraethylammonium para-tolylsulfonate), and tetraalkylammoniumcyanides (e.g. tetraethylammonium cyanide).

[0020] In yet another alternative embodiment, at least one base istypically present in carbonylation catalyst composition of the presentinvention. Suitable bases include, but are not limited to, alkali metalor alkaline-earth metal, guanidinium, or onium salts of basic oxides,hydroxides, mono or polyalkoxides with linear or branched alkyl chainshaving from about 1 to about 30 carbon atoms, aryloxides includingmonocyclic, polycyclic or fused polycyclic aromatic monohydroxy orpolyhydroxy compounds having from about 6 to about 30, and preferablyfrom about 6 to about 15 carbon atoms. Typical onium cations containorganic residues, which typically include C₁₋₂₀ alkyl, C₆₋₁₀ aryl, oralkyl-aryl combinations thereof. A second suitable class of basesincludes tertiary amines with organic residues which contain alkylresidues having from about 1 to about 20 carbon atoms, aryl residueshaving from about 6 to about 30, and preferably from about 6 to about 15carbon atoms, or alkyl-aryl combinations thereof. Typical bases include,but are not limited to, sodium hydroxide, lithium hydroxide, potassiumhydroxide, tetraalkylammonium hydroxides (e.g. tetramethylammoniumhydroxides, tetraethylammonium hydroxide, methyltributylammoniumhydroxide and tetrabutylammonium hydroxide) sodium phenoxide, lithiumphenoxide, potassium phenoxide, and tetraalkylammonium phenoxides (e.g.tetramethylammonium phenoxide, tetraethylammonium phenoxide,methyltributylammonium phenoxide and tetrabutylammonium phenoxide).

[0021] Typically, the first IOCC, comprising at least one Group 14 metalsource, is present in the amount of about 0.1 mole to about 150 moles ofGroup 14 metal source per mole of a Group 8, 9, or 10 catalyst. In oneembodiment between about 1 mole and about 100 moles of Group 14 IOCC permole of Group 8, 9 or 10 catalyst is used. In another alternativeembodiment between about 10 moles and about 70 moles of Group 14 IOCCper mole of Group 8, 9 or 10 catalyst is used. For example, when theGroup 8, 9, or 10 catalyst is palladium the molar ratio of lead relativeto palladium at the initiation of the reaction is typically betweenabout 10 moles and about 70 moles per mole of palladium.

[0022] In an embodiment which contains a second IOCC, the molar ratio ofthe second IOCC relative to the Group 8, 9, or 10 catalyst present inthe carbonylation catalyst composition at the initiation of the reactionis typically between about 0.1 mole and about 100 moles of second IOCCper mole of Group 8, 9, or 10 catalyst. In one embodiment the ratio of asecond IOCC relative to the Group 8, 9, or 10 catalyst at the initiationof the reaction is between about 1 mole and about 20 moles per mole ofGroup 8, 9 or 10 catalyst. For example, when the Group 8, 9, or 10catalyst is palladium, the molar ratio of the second IOCC (e.g., atitanium source, a manganese source, a copper source, or a ceriumsource) relative to palladium at the initiation of the reaction istypically between about 1 mole and about 100 moles per mole ofpalladium.

[0023] The molar ratio of the salt co-catalyst relative to Group 8, 9,or 10 catalyst present in the carbonylation catalyst composition at theinitiation of the reaction is between about 0.1 mole and about 10000moles per mole of Group 8, 9, or 10 catalyst. In one embodiment themolar ratio of the salt co-catalyst relative to Group 8, 9, or 10catalyst is between about 1 mole and about 1000 moles. For example, whenthe Group 8, 9 or 10 catalyst is palladium, the molar ratio of the saltco-catalyst relative to palladium at the initiation of the reaction istypically between about 1 mole and about 600 moles per mole ofpalladium.

[0024] The molar ratio of the base relative to the Group 8, 9, or 10catalyst at the initiation of the reaction is typically between about0.1 mole and about 1000 moles of base per mole of the Group 8, 9, or 10catalyst. In one embodiment, the molar ratio of the base relative to theGroup 8, 9, or 10 catalyst is between about 1 mole and about 600 molesper mole of Group 8, 9, or 10 catalyst. For example, when the Group 8, 9or 10 catalyst is palladium the molar ratio of the base to palladium istypically between about 1 mole and about 400 moles per mole ofpalladium.

[0025] The carbonylation method can be carried out in a variety ofreactor systems including, but not limited to, stirred vessels,autoclaves and bubble columns, each of which is capable of beingoperated under batch-liquid/batch-gas reactor conditions (i.e.batch/batch), batch-liquid/continuous-gas reactor conditions (i.e.batch/flow or semi-continuous), or continuous-liquid/continuous-gasreactor conditions (i.e.flow/flow). In one embodiment two or morereactors are typically employed in a cascade. In one embodiment about 2to about 15 reactors are used. When a reactor cascade is used instead ofan individual reactor, the separate gas addition preferably proceeds insuch a way that the optimal gas concentrations are ensured in each ofthe reactors. Due in part to the low solubility of carbon monoxide andoxygen in organic aromatic hydroxy compounds, such as phenol, it ispreferable that each reactor vessel be pressurized. A total pressure inthe range up to about 35 Megapascals (MPa) is used. In one embodimentthe reaction pressure is between about 0.5 MPa and about 14 MPa.

[0026] The reaction gases are typically reagent grade purity, andspecial care must be taken to ensure that no catalyst compositionpoisons are present as impurities in the gas sources. In one embodimentthe carbon monoxide and oxygen are introduced independently of eachother into the reactor vessel. In an alternative embodiment the carbonmonoxide and oxygen are introduced into the reactor vessel as a singlepremixed gas mixture comprising carbon monoxide and oxygen. Thecomposition of the reaction gases comprising carbon monoxide and oxygencan be varied in broad concentration ranges. For example the volumepercent oxygen in the gas mixtures can be up to about 0.1 volume % toabout 20 volume %. In one embodiment the volume % of oxygen in the gasmixture is between about 1% and about 9%. Gas sparging or mixing can beused to aid the reaction. Additional inert gases, such as nitrogen,helium, neon, argon, krypton, xenon, or any other gas which has nonegative effect on the carbonylation reaction can be added to thereactor vessel in order to dilute the carbon monoxide and oxygen gasmixture. For example, air is an acceptable substitute for pure oxygen.The concentration of inert gas in the reaction gas is typically up toabout 60 volume %. In one embodiment the volume % of inert gas is about0% to about 20% of the total gas volume.

[0027] Typical reaction temperatures are between about 50° C. and about150° C. In one embodiment the reaction temperature is between about 90°C. and about 110° C. Provisions are typically made for including adrying agent or a drying process step in the overall reaction method.Higher catalyst turnover numbers are typically obtained if water isremoved from the reaction mixture during the reaction.

[0028] The following examples are included to provide additionalguidance to those skilled in the art in practicing the claimedinvention. The examples provided are merely representative of the workthat contributes to the teaching of the present application.Accordingly, the following examples are not intended to limit theinvention, as defined in the appended claims, in any manner.

[0029] In the following examples, the aromatic carbonate produced isdiphenyl carbonate (DPC) and the Group 8, 9, or 10 metal utilized ispalladium. For convenience, the number of moles of DPC produced per moleof palladium charged to a reaction is referred to as the palladiumturnover number (Pd TON), and is used as an activity metric in thefollowing examples.

EXAMPLES 1-13

[0030] Carbonylation reactions were carried out in glass reactionvessels containing about 15 ppm to about 25 ppm of palladium(II)2,4-pentanedionate in phenol, IOCC combinations in equivalents versuspalladium, various salt co-catalyst components in equivalents versuspalladium, and sodium hydroxide in equivalents versus palladium.Titanium (Ti) was added as titanium(IV) oxide 2,4-pentanedionate,manganese (Mn) was added as manganese(III) 2,4-pentanedionate, copper(Cu) was added as copper(II) 2,4-pentanedionate, and cerium (Ce) wasadded as cerrium(III) 2,4-pentanedionate. The components were heated to100° C. for 3 hours in an atmosphere of about 6% to about 9% oxygen incarbon monoxide at about 11 megapascals. Amounts are in parts permillion (ppm) or equivalents (eq); TBA-Benzoate is tetrabutylammoniumbenzoate; NaOAc is sodium acetate; TBA-SO₄ is tetrabutylammoniumsulfate; TBA-NO₃ is tetrabutylammonium nitrate; TBA-BPh₄ istetrabutylammonium tetraphenylborate; TEA-tolSO₃ is tetraethylammoniumpara-tolylsulfonate; and TEA-SCN is tetraethylammonium cyanide. Averageresults of runs are given in Tables 1-5. TABLE 1 Pd PbO salt/ Pd Example(ppm) eq. vs. Pd eq. vs. Pd TON 1 25 50 NaOAc/ 479 400 2 25 50TBA-benzoate/ 872 400 3 25 50 TBA-SO₄/ 426  50 4 25 50 TBA-NO₃/ 62 400 525 50 TBA-BPh₄/ 48 400 6 25 50 TEA-tolSO₃/ 79  50 7 25 50 TEA-CN/ 84  50

[0031] TABLE 2 Pd PbO salt/ NaOH Pd Example (ppm) eq. vs. Pd eq. vs. PdEq. vs. Pd TON 8 25 50 NaOAc/ 200 202 400 9 25 50 TBA- 200 1028benzoate/ 400

[0032] TABLE 3 Pd PbO Ti salt/ Pd Example (ppm) eq. vs. Pd eq. vs. Pdeq. vs. Pd TON 10 25 50 6 NaOAc/ 273 400 11 25 50 6 TBA-benzoate/ 791400

[0033] TABLE 4 Pd PbO Ce salt/ Pd Example (ppm) eq. vs. Pd eq. vs. Pdeq. vs. Pd TON 12 25 50 6 NaOAc/ 258 400 13 25 50 6 TBA-benzoate/ 1049400

[0034] TABLE 5 Pd PbO 2^(nd) IOCC TMAOH salt/ Pd Example (ppm) eq. vs.Pd 2^(nd) IOCC eq. vs. Pd eq. vs. Pd eq. vs. Pd TON 14 15 100 Ti 18 400TBA-NO₃/ 1679 500 15 15 100 Ti 18 400 TBA-benzoate/ 1372 500 16 15 100Ti 18 400 TEA-tolSO₃/ 1499 500 17 15 100 Ce 12 400 TBA-benzoate/ 1767500 18 15 100 Ce 12 400 TEA-tolSO₃/ 2027 500 19 15 100 Cu 12 200TBA-benzoate/ 571 500 20 15 100 Cu 12 200 TBA-SO₄/ 809 500 21 15 100 Mn12 400 TBA-NO₃/ 959 500 22 15 100 Mn 12 400 TBA-benzoate/ 1349 500 23115 100 Mn 12 400 TEA-tolSO₃/ 1525 500

[0035] It will be understood that each of the elements described above,or two or more together, typically also find utility in applicationsdiffering from the types described herein. While the invention has beenillustrated and described as embodied in a method and catalystcomposition for producing aromatic carbonates, it is not intended to belimited to the details shown, since various modifications andsubstitutions can be made without departing in any way from the spiritof the present invention. For example, additional effective IOCCcompounds can be added to the reaction. As such, further modificationsand equivalents of the invention herein disclosed typically occur topersons skilled in the art using no more than routine experimentation,and all such modifications and equivalents are believed to be within thespirit and scope of the invention as defined by the following claims.

What is claimed is:
 1. A carbonylation catalyst composition comprisingthe following and any reaction products thereof: an effective amount ofat least one Group 8, 9, or 10 metal source; an effective amount of atleast one inorganic co-catalyst comprising a Group 14 element source;and an effective amount of at least one salt co-catalyst with an anionselected from the group consisting of carboxylate, benzoate, acetate,sulfate, nitrate, arylborate, alkylsulfonate, arylsulfonate, andcyanide; wherein the carbonylation catalyst composition is free of ahalide source.
 2. The carbonylation catalyst composition of claim 1,wherein the Group 8, 9, or 10 metal source is a palladium source.
 3. Thecarbonylation catalyst composition of claim 2, wherein the palladiumsource is palladium(II) 2,4-pentanedionate.
 4. The carbonylationcatalyst composition of claim 1, wherein the Group 14 inorganicco-catalyst is a lead source.
 5. The carbonylation catalyst compositionof claim 4, wherein the lead source is one member selected from thegroup consisting of lead(II) oxide, tetraethyllead(IV), and lead(II)phenoxide.
 6. The carbonylation catalyst composition of claim 1, whereinthe salt co-catalyst contains a cation selected from the groupconsisting of alkali metal cation, alkaline-earth metal cation,guanidinium, and onium cation.
 7. The carbonylation catalyst compositionof claim 6, wherein the salt co-catalyst is at least one member selectedfrom the group consisting of tetraalkylammonium or alkali metalcarboxylates, tetraalkylammonium sulfates, tetraalkylammonium nitrates,tetraarylammonium tetrarylborates, tetraalkylammonium sulfonates, andtetraalkylammonium cyanides.
 8. The carbonylation catalyst compositionof claim 7, wherein the salt co-catalyst is at least one member selectedfrom the group consisting of sodium acetate, tetrabutylammoniumbenzoate, tetrabutylammonium sulfate, tetrabutylammonium nitrate,tetrabutylammonium tetraphenylborate, tetraethylammoniumpara-tolylsulfonate, and tetraethylammonium cyanide.
 9. Thecarbonylation catalyst composition of claim 1, further comprising aneffective amount of at least one base.
 10. The carbonylation catalystcomposition of claim 9, wherein the base is at least one member selectedfrom the group consisting of basic oxides, hydroxides, alkoxides,aryloxides, and amines.
 11. The carbonylation catalyst composition ofclaim 10, wherein the base comprises at least one member selected fromthe group consisting of alkali metal hydroxides and alkaline-earth metalhydroxides.
 12. The carbonylation catalyst composition of claim 11,wherein the base is sodium hydroxide. 13 The carbonylation catalystcomposition of claim 10, wherein the base comprises at least one memberselected from the group consisting of onium hydroxide and guanidiniumhydroxide.
 14. The carbonylation catalyst composition of claim 13,wherein the base is a tetraalkylammonium hydroxide.
 15. Thecarbonylation catalyst composition of claim 14, wherein the base istetramethylammonium hydroxide.
 16. A carbonylation catalyst compositioncomprising the following and any reaction products thereof: an effectiveamount of palladium(II) 2,4-pentanedionate; an effective amount oflead(II) oxide; and an effective amount of at least one member selectedfrom the group consisting of sodium acetate, tetrabutylammoniumbenzoate, tetrabutylammonium sulfate, tetrabutylammonium nitrate,tetrabutylammonium tetraphenylborate, tetraethylammoniumpara-tolylsulfonate, and tetraethylammonium cyanide; wherein thecarbonylation catalyst composition is free of a halide source.
 17. Acarbonylation catalyst composition comprising the following and anyreaction products thereof: an effective amount of palladium(II)2,4-pentanedionate; an effective amount of lead(II) oxide; an effectiveamount of at least one compound selected from the group consisting ofsodium acetate, tetrabutylammonium benzoate, tetrabutylammonium sulfate,tetrabutylammonium nitrate, tetrabutylammonium tetraphenylborate,tetraethylammonium para-tolylsulfonate, and tetraethylammonium cyanide;and an effective amount of sodium hydroxide; wherein the carbonylationcatalyst composition is free of a halide source.
 18. A carbonylationcatalyst composition comprising the following and any reaction productsthereof: an effective amount of at least one Group 8, 9, or 10 metalsource; an effective amount of a first inorganic co-catalyst comprisingat least one Group 14 element source; an effective amount of at leastone second inorganic co-catalyst selected from the group consisting of aGroup 4 metal source, a Group 7 metal source, a Group 11 metal source,and a lanthanide element source; and an effective amount of at least onesalt co-catalyst with an anion selected from the group consisting ofcarboxylate, benzoate, acetate, sulfate, nitrate, arylborate,alkylsulfonate, arylsulfonate, and cyanide; wherein the carbonylationcatalyst composition is free of a halide source.
 19. The carbonylationcatalyst composition of claim 18, wherein the Group 8, 9, or 10 metalsource is a palladium source.
 20. The carbonylation catalyst compositionof claim 19, wherein the palladium source is palladium(II)2,4-pentanedionate.
 21. The carbonylation catalyst composition of claim18, wherein the first inorganic co-catalyst is a lead source.
 22. Thecarbonylation catalyst composition of claim 21, wherein the lead sourceis one member selected from the group consisting of lead(II) oxide,tetraethyllead(IV), and lead(II) phenoxide.
 23. The carbonylationcatalyst composition of claim 18, wherein the second inorganicco-catalyst is at least one member selected from the group consisting ofa titanium source, a manganese source, a copper source, and a lanthanidesource.
 24. The carbonylation catalyst composition of claim 23, whereinthe second inorganic co-catalyst is at least one member selected fromthe group consisting of titanium(IV) oxide 2,4-pentanedionate,manganese(III) 2,4-pentanedionate, copper(II) 2,4-pentanedionate, andcerium(III) 2,4-pentanedionate.
 25. The carbonylation catalystcomposition of claim 18, wherein the salt co-catalyst contains a cationselected from the group consisting of an alkali metal cation,alkaline-earth metal cation, guanidinium cation, and an onium cation.26. The carbonylation catalyst composition of claim 25, wherein the saltco-catalyst is at least one member selected from the group consisting oftetraalkylammonium or alkali metal carboxylates, tetraalkylammoniumsulfates, tetraalkylammonium nitrates, tetraalkylammoniumtetraarylborates, tetraalkylammonium sulfonates, and tetraalkylammoniumcyanides.
 27. The carbonylation catalyst composition of claim 26,wherein the salt co-catalyst is at least one member selected from thegroup consisting of sodium acetate, tetrabutylammonium benzoate,tetrabutylammonium sulfate, tetrabutylammonium nitrate,tetrabutylammonium tetraphenylborate, tetraethylammoniumpara-tolylsulfonate, and tetraethylammonium cyanide.
 28. Thecarbonylation catalyst composition of claim 18, further comprising abase.
 29. The carbonylation catalyst composition of claim 28, whereinthe base is at least one member selected from the group consisting ofbasic oxides, hydroxides, alkoxides, aryloxides, and amines.
 30. Thecarbonylation catalyst composition of claim 29, wherein the base is onemember selected from the group consisting of hydroxides andalkaline-earth metal hydroxide.
 31. The carbonylation catalystcomposition of claim 30, wherein the base is sodium hydroxide.
 32. Thecarbonylation catalyst composition of claim 29, wherein the basecomprises at least one member selected from the group consisting ofonium hydroxides and guanidinium hydroxides.
 33. The carbonylationcatalyst composition of claim 32, wherein the base is atetraalkylammonium hydroxide.
 34. The carbonylation catalyst compositionof claim 33, wherein the base is tetramethylammonium hydroxide.
 35. Acarbonylation catalyst composition comprising the following and anyreaction products thereof: an effective amount of palladium(II)2,4-pentanedionate; an effective amount of lead(II) oxide; an effectiveamount of at least one member selected from the group consisting oftitanium(IV) oxide 2,4-pentanedionate, manganese(III)2,4-pentanedionate, copper(II) 2,4-pentanedionate, and cerium(III)2,4-pentanedionate; and an effective amount of at least one memberselected from the group consisting of sodium acetate, tetrabutylammoniumbenzoate, tetrabutylammonium sulfate, tetrabutylammonium nitrate,tetrabutylammonium tetraphenylborate, tetraethylammoniumpara-tolylsulfonate, and tetraethylammonium cyanide; wherein thecarbonylation catalyst composition is free of a halide source.
 36. Acarbonylation catalyst composition comprising the following and anyreaction products thereof: an effective amount of palladium(II)2,4-pentanedionate; an effective amount of lead(II) oxide; an effectiveamount of at least one member selected from the group consisting oftitanium(IV) oxide 2,4-pentanedionate, manganese(III)2,4-pentanedionate, copper(II) 2,4-pentanedionate, and cerium(III)2,4-pentanedionate; an effective amount of at least one member selectedfrom the group consisting of sodium acetate, tetrabutylammoniumbenzoate, tetrabutylammonium sulfate, tetrabutylammonium nitrate,tetrabutylammonium tetraphenylborate, tetraethylammoniumpara-tolylsulfonate, and tetraethylammonium cyanide; and an effectiveamount of sodium hydroxide; wherein the carbonylation catalystcomposition is free of a halide source.
 37. A method for carbonylatingan aromatic hydroxy compound, said method comprising the step ofcontacting at least one aromatic hydroxy compound with oxygen and carbonmonoxide in the presence of a carbonylation catalyst compositioncomprising the following and any reaction products thereof: an effectiveamount of at least one Group 8, 9, or 10 metal source; an effectiveamount of at least one inorganic co-catalyst comprising a Group 14element source; and an effective amount of at least one salt co-catalystwith an anion selected from the group consisting of carboxylate,benzoate, acetate, sulfate, nitrate, arylborate, alkylsulfonate,arylsulfonate, and cyanide; wherein the carbonylation catalystcomposition is free of a halide source.
 38. The method of claim 37,wherein the Group 8, 9, or 10 metal source is a palladium source. 39.The method of claim 38, wherein the palladium source is palladium(II)2,4-pentanedionate.
 40. The method of claim 38, wherein the inorganicco-catalyst is a lead source.
 41. The method of claim 40, wherein thelead source is one member selected from the group consisting of lead(II)oxide, tetraethyllead(IV), and lead(II) phenoxide.
 42. The method ofclaim 37, wherein the salt co-catalyst contains a cation selected fromthe group consisting of alkali metal cation, alkaline-earth metalcation, guanidinium cation, and onium cation.
 43. The method of claim42, wherein the salt co-catalyst is at least one member selected fromthe group consisting of tetraalkylammonium or alkali metal carboxylates,tetraalkylammonium sulfates, tetraalkylammonium nitrates,tetraarylammonium tetrarylborates, tetraalkylammonium sulfonates, andtetraalkylammonium cyanides.
 44. The method of claim 43, wherein thesalt co-catalyst is at least one member selected from the groupconsisting of sodium acetate, tetrabutylammonium benzoate,tetrabutylammonium sulfate, tetrabutylammonium nitrate,tetrabutylammonium tetraphenylborate, tetraethylammoniumpara-tolylsulfonate, and tetraethylammonium cyanide.
 45. The method ofclaim 37, further comprising at least one base.
 46. The method of claim45, wherein the base is at least one member selected from the groupconsisting of basic oxides, hydroxides, alkoxides, aryloxides, andamines.
 47. The method of claim 46, wherein the base is one memberselected form the group consisting of alkali metal hydroxides andalkaline-earth metal hydroxides.
 48. The method of claim 47, wherein thebase is sodium hydroxide.
 49. The method of claim 46, wherein the baseis at lest one member selected from the group consisting of oniumhydroxide and guanidinium hyrdroxide.
 50. The method of claim 49,wherein the base is a tetraalkylammonium hydroxide.
 51. The method ofclaim 50, wherein the base is tetramethylammonium hydroxide.
 52. Amethod for carbonylating an aromatic hydroxy compound, said methodcomprising the step of contacting at least one aromatic hydroxy compoundwith oxygen and carbon monoxide in the presence of a carbonylationcatalyst composition comprising the following and any reaction productsthereof: an effective amount of palladium(II) 2,4-pentanedionate; aneffective amount of lead(II) oxide; and an effective amount of at leastone member selected from the group consisting of sodium acetate,tetrabutylammonium benzoate, tetrabutylammonium sulfate,tetrabutylammonium nitrate, tetrabutylammonium tetraphenylborate,tetraethylammonium para-tolylsulfonate, and tetraethylammonium cyanide;wherein the carbonylation catalyst composition is free of a halidesource. 53 The method of claim 52, wherein the aromatic hydroxy compoundis phenol. 54 A method for carbonylating an aromatic hydroxy compound,said method comprising the step of contacting at least one aromatichydroxy compound with oxygen and carbon monoxide in the presence of acarbonylation catalyst composition comprising the following and anyreaction products thereof: an effective amount of palladium(II)2,4-pentanedionate; an effective amount of lead(II) oxide; an effectiveamount of at least one member selected from the group consisting ofsodium acetate, tetrabutylammonium benzoate, tetrabutylammonium sulfate,tetrabutylammonium nitrate, tetrabutylammonium tetraphenylborate,tetraethylammonium para-tolylsulfonate, and tetraethylammonium cyanide;and an effective amount of sodium hydroxide; wherein the carbonylationcatalyst composition is free of a halide source.
 55. The method of claim54, wherein the aromatic hydroxy compound is phenol.
 56. A method forcarbonylating an aromatic hydroxy compound, said method comprising thestep of contacting at least one aromatic hydroxy compound with oxygenand carbon monoxide in the presence of a carbonylation catalystcomposition comprising the following and any reaction products thereof:an effective amount of at least one Group 8, 9, or 10 metal source; aneffective amount of a first inorganic co-catalyst comprising at leastone Group 14 element source; an effective amount of at least one secondinorganic co-catalyst selected from the group consisting of a Group 4metal source, a Group 7 metal source, a Group 11 metal source, and alanthanide element source; and an effective amount of at least one saltco-catalyst with an anion selected from the group consisting ofcarboxylate, benzoate, acetate, sulfate, nitrate, arylborate,alkylsulfonate, arylsulfonate, and cyanide; wherein the carbonylationcatalyst composition is free of a halide source.
 57. The method of claim56, wherein the Group 8, 9, or 10 metal source is a palladium source.58. The method of claim 57, wherein the palladium source ispalladium(II) 2,4-pentanedionate.
 59. The method of claim 56, whereinthe first inorganic co-catalyst is a lead source.
 60. The method ofclaim 59, wherein the lead source is a member selected from the groupconsisting of lead(II) oxide, tetraethyllead(IV), and lead(II)phenoxide.
 61. The method of claim 59, wherein the second inorganicco-catalyst is at least one member selected from the group consisting ofa titanium source, a manganese source, a copper source, and a lanthanidesource.
 62. The method of claim 61, wherein the second inorganicco-catalyst is at least one member selected from the group consisting oftitanium(IV) oxide 2,4-pentanedionate, manganese(III)2,4-pentanedionate, copper(II) 2,4-pentanedionate, and cerium(III)2,4-pentanedionate.
 63. The method of claim 56, wherein the saltco-catalyst contains a cation selected from the group consisting ofalkali metal cation, alkaline-earth metal cation, guanidinium cation andonium cation.
 64. The method of claim 63, wherein the salt co-catalystis at least one member selected from the group consisting oftetraalkylammonium or alkali metal carboxylates, tetraalkylammoniumsulfates, tetraalkylammonium nitrates, tetraalkylammoniumtetraarylborates, tetraalkylammonium sulfonates, and tetraalkylammoniumcyanides.
 65. The method of claim 64, wherein the salt co-catalyst is atleast one member selected from the group consisting of sodium acetate,tetrabutylammonium benzoate, tetrabutylammonium sulfate,tetrabutylammonium nitrate, tetrabutylammonium tetraphenylborate,tetraethylammonium para-tolylsulfonate, and tetraethylammonium cyanide.66. The method of claim 56, further comprising a base.
 67. The method ofclaim 66, wherein the base is at least one member selected from thegroup consisting of basic oxides, hydroxides, alkoxides, aryloxides, andamines.
 68. The method of claim 67, wherein the base is one memberselected from the group consisting of alkali metal hydroxide andalkaline-earth metal hydroxides.
 69. The method of claim 68, wherein thebase is sodium hydroxide.
 70. The method of claim 67, wherein the baseis at least one member selected from the group consisting of oniumhydroxide and guanidinium hydroxide.
 71. The method of claim 70, whereinthe base is a tetraalkylammonium hydroxide.
 72. The method of claim 71,wherein the base is tetramethylammonium hydroxide.
 73. A method forcarbonylating an aromatic hydroxy compound, said method comprising thestep of contacting at least one aromatic hydroxy compound with oxygenand carbon monoxide in the presence of a carbonylation catalystcomposition comprising the following and any reaction products thereof:an effective amount of palladium(II) 2,4-pentanedionate; an effectiveamount of lead(II) oxide; an effective amount of at least one memberselected from the group consisting of titanium(IV) oxide2,4-pentanedionate, manganese(III) 2,4-pentanedionate, copper(II)2,4-pentanedionate, and cerium(II1) 2,4-pentanedionate; and an effectiveamount of at least one member selected from the group consisting ofsodium acetate, tetrabutylammonium benzoate, tetrabutylammonium sulfate,tetrabutylammonium nitrate, tetrabutylammonium tetraphenylborate,tetraethylammonium para-tolylsulfonate, and tetraethylammonium cyanide;wherein the carbonylation catalyst composition is free of a halidesource.
 74. The method of claim 73, wherein the aromatic hydroxycompound is phenol.
 75. A method for carbonylating an aromatic hydroxycompound, said method comprising the step of contacting at least onearomatic hydroxy compound with oxygen and carbon monoxide in thepresence of a carbonylation catalyst composition comprising thefollowing and any reaction products thereof: an effective amount ofpalladium(II) 2,4-pentanedionate; an effective amount of lead(II) oxide;an effective amount of at least one member selected from the groupconsisting of titanium(IV) oxide 2,4-pentanedionate, manganese(III)2,4-pentanedionate, copper(II) 2,4-pentanedionate, and cerium(III)2,4-pentanedionate; an effective amount of at least one member selectedfrom the group consisting of sodium acetate, tetrabutylammoniumbenzoate, tetrabutylammonium sulfate, tetrabutylammonium nitrate,tetrabutylammonium tetraphenylborate, tetraethylammoniumpara-tolylsulfonate, and tetraethylammonium cyanide; and an effectiveamount of sodium hydroxide; wherein the carbonylation catalystcomposition is free of a halide source.
 76. The method of claim 75,wherein the aromatic hydroxy compound is phenol.